Mass fluxes of xenobiotics below cities: challenges in urban hydrogeology

Urban areas are the focus of major ecological, social and economical activity. They are thus also prime locations of increasing conflict with regard to water use and water protection. As a direct and/or indirect consequence of urban land use and human activity, urban water systems are frequently polluted with organic contaminants including waste water-born xenobiotics such as pharmaceuticals, personal care products (collectively known as PPCPs) and endocrine-active substances. This study reviews new integrated methodologies including flux calculations as well as chemical investigations for determining the impact of human activities on urban water systems and on processes within the urban watershed. The use of indicator substances, representing different contaminant sources and pathways, integral pumping tests and mass balance approaches are suitable alternatives within these environments. The issues are explored using contaminant mass balance examples from Halle/Saale and Leipzig, Germany.     

The BEAM-project: prediction and assessment of mixture toxicities in the aquatic environment

Freshwater and marine ecosystems are exposed to various multi-component mixtures of pollutants. Nevertheless, most ecotoxicological research and chemicals regulation focus on hazard and exposure assessment of individual substances only, the problem of chemical mixtures in the environment is ignored to a large extent. In contrast, the assessment of combination effects has a long tradition in pharmacology, where mixtures of chemicals are specifically designed to develop new products, e.g. human and veterinary drugs or agricultural and non-agricultural pesticides. In this area, two concepts are frequently used and are thought to describe fundamental relationships between single substance and mixture effects: Independent Action (Response Addition) and Concentration Addition. The question, to what extent these concepts may also be applied in an ecotoxicological and regulatory context may be considered a research topic of major importance, as the concepts would allow to make use of already existing single substance toxicity data for the predictive assessment of mixture toxicities. Two critical knowledge gaps are identified: (a) There is a lack of environmental realism, as a huge part of our current knowledge about the applicability of the concepts is restricted to artificial situations with respect to mixture composition or biological effect assessment. (b) The knowledge on what exactly is needed for using the concepts as tools for the predictive mixture toxicity assessment is insufficient. Both gaps seriously hamper the necessary, scientifically sound consideration of mixture toxicities in a regulatory context.In this paper, the two concepts will be briefly introduced, the necessity of considering the toxicities of chemical mixtures in the environment will be demonstrated and the applicability of Independent Action and Concentration Addition as tools for the prediction and assessment of mixture toxicities will be discussed. An overview of the specific aims and approaches of the BEAM project to fill in the identified knowledge gaps is given and first results are outlined.     

Carbon Sequestration and Release from Antarctic Lakes: Lake Vida and West Lake Bonney (McMurdo Dry Valleys)

Perennial ice covers on many Antarctic lakes have resulted in high lake inorganic carbon contents. The objective of this paper was to evaluate and compare the brine and CO₂ chemistries of Lake Vida (Victoria Valley) and West Lake Bonney (Taylor Valley), two lakes of the McMurdo Dry Valleys (East Antarctica), and their potential consequences during global warming. An existing geochemical model (FREZCHEM-15) was used to convert measured molarity into molality needed for the FREZCHEM model, and this model added a new algorithm that converts measured DIC into carbonate alkalinity needed for the FREZCHEM model. While quite extensive geochemical information exists for ice-covered Taylor Valley lakes, such as West Lake Bonney, only limited information exists for the recently sampled brine of >25 m ice-thick Lake Vida. Lake Vida brine had a model-calculated pCO₂ = 0.60 bars at the field pH (6.20); West Lake Bonney had a model-calculated pCO₂ = 5.23 bars at the field pH (5.46). Despite the high degree of atmospheric CO₂ supersaturation in West Lake Bonney, it remains significantly undersaturated with the gas hydrate, CO₂·6H₂O, unless these gas hydrates are deep in the sediment layer or are metastable having formed under colder temperatures or greater pressures. Because of lower temperatures, Lake Vida could start forming CO₂·6H₂O at lower pCO₂ values than West Lake Bonney; but both lakes are significantly undersaturated with the gas hydrate, CO₂·6H₂O. For both lakes, simulation of global warming from current subzero temperatures (?13.4 °C in Lake Vida and ?4.7 °C in West Lake Bonney) to 10 °C has shown that a major loss of solution-phase carbon as CO₂ gases and carbonate minerals occurred when the temperatures rose above 0 °C and perennial ice covers would disappear. How important these Antarctic CO₂ sources will be for future global warming remains to be seen. But a recent paper has shown that methane increased in atmospheric concentration due to deglaciation about 10,000 years ago. So, CO₂ release from ice lakes might contribute to atmospheric gases in the future.     

Calcification depth and spatial distribution of Thoracosphaera heimii cysts: Implications for palaeoceanographic reconstructions

For the optimal use in palaeoceanographic studies of the stable oxygen isotopic signal and elemental composition of the calcareous photosynthetic dinoflagellate Thoracosphaera heimii, it is essential to gain detailed information about its calcification depth and spatial distribution. We therefore studied the vertical and horizontal distribution patterns of T. heimii in the upper water column (0–200 m) along three transects: an inshore–offshore gradient off Cape Blanc (CB), a south–north transect from CB to the Portuguese coast and a north–south transect off Tanzania. We compared concentrations of living cysts (cells with cell content) with chlorophyll-a, salinity and temperature measurements at the sampling depth. In order to explore the seasonal variability in cyst production, three transect off CB were sampled at three different times of the year.Living T. heimii cysts were found in the upper 160 m of the water column with highest concentrations in the photic zone indicating that the calcification of T. heimii occurs in the upper part of the water column. Maximal abundances of living cysts were found relatively often in or just above the deep chlorophyll maximum (DCM), the depth of which varies regionally from about 20–40 m off CB to about 80 m off Tanzania and along the transect from CB to the Portuguese Coast. However, there was no significant correlation at the 95% confidence level between the cyst concentrations and temperature, salinity and chlorophyll-a concentrations at the sampling depths observed.In both the Atlantic and Indian Oceans, the highest abundances of T. heimii were observed in regions where the upper water masses contained relatively low nutrient concentrations that are influenced only sporadically, or not at all, by enhanced photic zone mixing related to the presence of upwelling cells or river outflow plumes at or close to the sampling sites. The seasonal production of cysts by T. heimii appears to be negatively related to the presence of upwelling filaments across the sampling sites. Our study suggests that turbulence of the upper water masses is a major environmental factor influencing T. heimii production.     

Alkaline fluid circulation in ultramafic rocks and formation of nucleotide constituents: a hypothesis

Seawater is constantly circulating through oceanic basement as a low-temperature hydrothermal fluid (<150°C). In cases when ultramafic rocks are exposed to the fluids, for instance during the initial phase of subduction, ferromagnesian minerals are altered in contact with the water, leading to high pH and formation of secondary magnesium hydroxide, among other – brucite, that may scavenge borate and phosphate from seawater. The high pH may promote abiotic formation of pentoses, particularly ribose. Pentoses are stabilized by borate, since cyclic pentoses form a less reactive complex with borate. Analyses have shown that borate occupies the 2' and 3' positions of ribose, thus leaving the 5' position available for reactions like phosphorylation. The purine coding elements (adenine, in particular) of RNA may be formed in the same general hydrothermal environments of the seafloor.     

Identification of Atlantic water inflow on the north Svalbard shelf during the Holocene

Nordaustlandet is located in the northeastern part of the Svalbard archipelago, within the northernmost reach of the West Spitsbergen Current. This current transports Atlantic water to the Arctic Ocean along the western and northern Svalbard margins. This region is well-suited for reconstructing the history of changing Atlantic water inflow to the Arctic Ocean. We studied the marine sediment core HH12-04-GC from Rijpfjorden. Benthic foraminiferal assemblages and sedimentological data are combined to reconstruct the palaeoenvironment of the fjord from the end of the last local deglaciation to the late Holocene. The local deglaciation, between 11.3 and 10.6 cal ka bp , was dominated by active glacier calving processes, associated with a strong inflow of Atlantic water. This led to the establishment of glaciomarine conditions. The Holocene was initially characterised by a relatively stable and warm environment associated with a strong contribution of Atlantic water. Glaciomarine influence progressively decreases after 9.7 cal ka bp and the Atlantic water contribution increases. The late Holocene displayed a similar environment to today, with the influence of glaciomarine conditions and limited Atlantic water inflow. These results confirm that Atlantic water inflows made a continuous contribution to northern Nordaustlandet throughout the postglacial period.     

Hyperspectral mapping of alteration assemblages within a hydrothermal vug at the Haughton impact structure,Canada

Meteorite impacts on Earth and Mars can generate hydrothermal systems that alter the primary mineralogies of rocks and provide suitable environments for microbial colonization. We investigate a calcite–marcasite‐bearing vug at the ~23 km diameter Haughton impact structure, Devon Island, Nunavut, Canada, using imaging spectroscopy of the outcrop in the field (0.65–1.1 μm) and samples in the laboratory (0.4–2.5 μm), point spectroscopy (0.35–2.5 μm), major element chemistry, and X‐ray diffraction analyses. The mineral assemblages mapped at the outcrop include marcasite; marcasite with minor gypsum and jarosite; fibroferrite and copiapite with minor gypsum and melanterite; gypsum, Fe³⁺ oxides, and jarosite; and calcite, gypsum, clay, microcline, and quartz. Hyperspectral mapping of alteration phases shows spatial patterns that illuminate changes in alteration conditions and formation of specific mineral phases. Marcasite formed from the postimpact hydrothermal system under reducing conditions, while subsequent weathering oxidized the marcasite at low temperatures and water/rock ratios. The acidic fluids resulting from the oxidation collected on flat‐lying portions of the outcrop, precipitating fibroferrite + copiapite. That assemblage then likely dissolved, and the changing chemistry and pH resulting from interaction with the calcite‐rich host rock formed gypsum‐bearing red coatings. These results have implications for understanding water–rock interactions and habitabilities at this site and on Mars.